Renne Alissa, Luo Lindi, Jarow Jonathan, Wright William W, Brown Terry R, Chen Haolin, Zirkin Barry R, Friesen Marlin D
Department of Environmental Health Sciences, Johns Hopkins Bloomberg School of Public Health, 615 N Wolfe St, Baltimore, MD 21205-2179, USA.
J Androl. 2012 Jul-Aug;33(4):691-8. doi: 10.2164/jandrol.111.014977. Epub 2011 Oct 20.
An isotope dilution mass spectrometry method has been developed for the simultaneous measurement of picolinoyl derivatives of testosterone (T), dihydrotestosterone (DHT), 17β-estradiol (E(2)), and 5α-androstan-3α,17β-diol (3α-diol) in rat intratesticular fluid. The method uses reversed-phase high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Following derivatization of 10-μL samples of testicular fluid with picolinoyl chloride hydrochloride, the samples were purified by solid phase extraction before analysis. The accuracy of the method was satisfactory for the 4 analytes at 3 concentrations, and both inter- and intraday reproducibility were satisfactory for T, DHT, and E(2). Measurements of intratesticular T concentrations in a group of 8 untreated adult rats by this method correlated well with measurements of the same samples by radioimmunoassay. As in men, there was considerable rat-to-rat variability in T concentration, despite the fact that the rats were inbred. Although its levels were more than an order of magnitude lower than those of T, DHT was measured reliably in all 8 intratesticular fluid samples. DHT concentration also varied from rat to rat and was highly correlated with T levels. The levels of E(2) and 3α-diol also were measurable. The availability of a sensitive method by which to measure steroids accurately and rapidly in the small volumes of intratesticular fluid obtainable from individual rats will make it possible to examine the effects, over time, of such perturbations as hormone and drug administration and environmental toxicant exposures on the intratesticular hormonal environment of exposed individual males and thereby to begin to understand differences in response between individuals.
已开发出一种同位素稀释质谱法,用于同时测定大鼠睾丸内液中睾酮(T)、双氢睾酮(DHT)、17β-雌二醇(E₂)和5α-雄甾烷-3α,17β-二醇(3α-二醇)的吡啶甲酰基衍生物。该方法采用反相高效液相色谱与电喷雾电离串联质谱联用。用盐酸吡啶甲酰氯对10μL睾丸液样品进行衍生化后,在分析前通过固相萃取对样品进行纯化。该方法对3种浓度的4种分析物的准确度令人满意,T、DHT和E₂的日内和日间重现性均令人满意。用该方法对一组8只未处理的成年大鼠的睾丸内T浓度进行测量,与用放射免疫分析法对相同样品的测量结果相关性良好。与人类一样,尽管这些大鼠是近亲繁殖的,但T浓度在大鼠之间仍存在相当大的差异。尽管其水平比T低一个数量级以上,但在所有8个睾丸内液样品中均能可靠地检测到DHT。DHT浓度在大鼠之间也有所不同,并且与T水平高度相关。E₂和3α-二醇的水平也可测量。有了一种灵敏的方法,可以准确快速地测量从个体大鼠获得的少量睾丸内液中的类固醇,这将有可能随着时间的推移,研究激素和药物给药以及环境毒物暴露等干扰因素对暴露个体雄性睾丸内激素环境的影响,从而开始了解个体之间反应的差异。